DE1261262B - Process for the catalytic conversion of a hydrocarbon feed - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN 4MTQ & PATENT OFFICE

EDITORIAL

Int. CL:

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German class: 23 b - 1/04

1,261,262
S77500IVd / 23b
January 11, 1962
15th February 1968

The invention relates to a process for the catalytic conversion of a hydrocarbon feed by bringing the hydrocarbons into contact with under conversion conditions a catalyst.

There are many approaches to the catalytic conversion of hydrocarbons, e.g. B. for cracking high-boiling hydrocarbons, such as gas oils or distillation residues, known in which on most common acidic catalysts are used,

It is Z. B. known cracking catalysts by acid treatment of natural aluminum hydrosilicates to produce, the bentonites used as the starting material of all being soluble in acid Fractions practically completely freed and then dissolved with the calculated amount Impregnated aluminum compound and thermally or chemically decomposed it on the contact material will.

When using the known acidic catalysts for the catalytic conversion of hydrocarbons however, there are various disadvantages, in particular due to the lack of thermal stability, lack of activity and lack of mechanical strength can be attributed to.

Furthermore, a method for the catalytic cracking of high-boiling hydrocarbons is known in which Gas oil at a temperature above 454 ° C with a by calcining a synthetic Zeolite gel prepared catalyst is brought into contact and wherein the catalyst following Composition has:

13 percent by weight Na ₂ O,
22 percent by weight Al ₂ O ₃ and 65 percent by weight SiO ₂ .

Furthermore, a process for the production of relatively granular and relatively fine spherical absorbent contact masses from kaolin clay is known, wherein the kaolin clay is treated with sulfuric acid and the treated mass is allowed to age with colorless mineral oil while maintaining a temperature of 104 to 204 ^° C. for 1 to 24 hours , then separating essentially all of the clay mass from accumulated fines, removing sulphate from the mass by calcining at a temperature of about 482 to 871 ° C, forming an aqueous slurry of the fine particles which were separated from the clay mass, the aqueous slurry in white oil within a temperature range of 121 to 260 ⁰ C with the formation of spherical particles, which are much smaller than the granular process for catalytic conversion
a hydrocarbon feed

Applicant:

Mobil Oil Corporation,
New York, NY (V. St. A.)

Representative:

Dr. E. Wiegand

and Dipl.-Ing. W. Niemann, patent attorneys,

8000 Munich 15, Nussbaumstr. 10

Named as inventor:
Vincent Joseph Frilette, Erlton, NJ;
Charles Joseph Plank, Woodbury, NJ;
Edward Joseph Rosinski, Sewell, NJ;
Paul Burg Weisz, Media, Pa. (V. St. A.)

Claimed priority:
V. St. v. America December 21, 1961
(161 241)

Masses are dispersed, and finally the sulfate from the spherical particles by calcining at a temperature of about 482 to 871 ° C.

Furthermore, a method for improving hydrocarbons is known in which a hydrocarbon stream in a reaction zone at elevated temperature with a crystalline metallic Aluminum silicate catalyst which has uniform pore openings in the range of about 6 to 15 Å, is brought into contact.

Finally, a method for improving hydrocarbons is known in which a hydrocarbon stream is brought into contact at elevated temperature with a hydrocarbon conversion catalyst, which consists of metals and compounds of the platinum group, oxides of molybdenum, chromium, tungsten, vanadium, nickel, copper and cobalt molybdate and their Mixtures, which are deposited on a crystalline zeolite molecular sieve made of aluminum silicate as a base, which has uniform pore openings between about 6 and 15 Å, and wherein the molecular sieve does not contain _{more than 10% sodium, calculated as Na 2 O.}

Even when using the known clay and zeolite catalysts for catalytic conversion

809 508/314

3 4

of hydrocarbons there is a certain weight of 0.25 equivalents per gram atom of aluminum

problems. There may be limited yields, there are no other cations

of gasoline for a given yield of coke from metals of Group IA of the Periodic Table

obtain. In addition, the service life of this catalytic converter is associated with the aluminum silicate. With connecting lysers often low because they quickly disintegrate from drying, washing and other intermediates

and in the presence of steam, in particular, this product is, as has been shown,

which become inactive at high temperatures. Clay- exceptionally active as a catalyst for carbon

Catalysts are often only moderately active and convert hydrogen.

show a decrease in the activity of the catalysts together with a longer service life. The aluminum silicate cannot settle with one

The object of the invention is in particular the sheep aqueous or aqueous liquid agents, eg. B. a

a simple and economical process of gas, a polar solvent or a water

for the catalytic conversion of a hydrocarbon solution containing the desired hydrogen ion or

Substance loading by contacting the carbon ammonium ion which can be converted into a hydrogen ion lenhydrogen under conversion conditions with 15 and at least one soluble in the liquid agent

contains a highly active catalyst with a wide range of metal salts, are brought into contact,

application area. The aluminum silicate can alternate with first

According to the invention, a liquid agent containing a hydrogen ion or is used as a catalyst

at least partially crystalline aluminum silicate uses an ammonium that can be converted into a hydrogen ion, which contains 0.5 to 1.0 equivalents per gram-20 ion, and then with a liquid agent,

atom aluminum, in contact with ions of positive valence that contain at least one metal salt

standing from 0.01 to 0.99 equivalents of hydrogen. Similarly, it can

ions per gram atom of aluminum and 0.99 to aluminum silicate initially with a liquid agent,

0.01 equivalents of cations of metals containing at least one metal salt, and then groups IB to VIII of the Periodic Table 25 with a liquid agent containing a hydrogen ion

per gram atom of aluminum. or an ion convertible into a hydrogen ion

Preferably, an aluminum silicate is used, or contains a mixture of both, in contact

that 0.8 to 1.0 equivalents of the ions of positive valence are brought. For reasons of economy

contains aluminum per gram atom. and because of the easy processing option In the method according to the invention to 30 in mass production with either continuous

The catalysts used have a wide range of specks or batches of treatment using water as an agent

center of catalytic activity. You can in except-preferred.

usually low concentrations used For the same reasons, organic solutions and allow many carbons to be carried out are less preferred. B. Krak- 35, provided that the solvent ionization, alkylation, dealkylation, isomerization tion of the acid, the ammonium compound and the and reforming of hydrocarbons allows prak- metallic salt. Typical solvents tables and controllable speeds and with are cyclic and acyclic ethers, such as dioxane, much lower temperatures than they had to be used earlier tetrahydrofuran, ethyl ether, diethyl ether, diisopropyl alcohol. In the catalytic Krak- 4 ° pyläther od. The like., Ketones such as acetone and methylene of hydrocarbon oils in hydrocarbon oils, esters such as ethyl acetate, propyl acetate, aluminum products of lower molecular weight, alcohols such as ethanol, propanol, butanol, etc., and the Reaction rates per unit volume of catalyst, various solvents, such as dimethylformamide, lysator, which in the process according to the invention The hydrogen ion, the metal cation or the can be obtained, up to a thousand times 45 ■ ammonium ion can be used in an amount in the liquid of the best proposed so far silicon agent be present, the speeds achieved within wide limits containing catalysts. varies, depending on the pH. The highly liquid agent to be used according to the invention. If the aluminosilicate active catalysts are aluminosilicate composite material has a molar ratio of silica compositions of a strongly acidic nature as a result of treatment to alumina of more than about 5.0, treatment with a liquid agent which can at least be a hydrogen ion contain a metallic cation and a hydrogen ion or metal cation, an ammonium ion or a mixture thereof containing an ion that can be converted into a hydrogen ion, equivalent to a pH value in the holds. Inorganic and organic acids range from less than 1.0 to about 12.0. In general, sources of hydrogen ions are metal. The pH values for liquid salts, those of metal cations, and ammonium compounds, which are 'a metallic cation and / or compounds, which of cations which are in hydrogen-ammonium ion lie within these limits Contain from 4.0 to 10.0 and can be converted into ions. This consists of preferably between a pH value of 4.5 and 8.5. For liquid agents that contain a hydrogen ion alone product is an activated, crystalline and / or 60 or with a metallic cation, is amorphous aluminum silicate, the core structure of which has a pH of less than 1.0 up to has been modified only to approximately such an extent, 7.0, and preferably within the range of protons and metallic cations thereon from less than 1.0 up to 4.5. When the molar mixture is adsorbed or ionically bound to it. The activated aluminum silicate contains at least ⁶ 5 danger 2.2 and less than about 5.0, the 0.5 equivalent of ions of positive valence per gram pH for the liquid agents that contain a Hydrogen atom aluminum. Except for alkali metal cations containing ion or a metal cation, from 3.8 to 8.5. than impurities in an amount less than

5 6

combination with metallic cations is used. A solution of the ions of positive valence in the, the pH value of 4.5 to 9.5 and the preferred form of molten material, vapor, aqueous, is within the limits of 4.5 to 8.5. Whether or not aqueous solutions can slowly be passed through the aluminum silicate material a molar ratio of a fixed bed of aluminum silicate of silicon to aluminum of less than 5. If desired, a hydrothermal hazard may be 3.0, the preferred agent is a liquid treatment or a correspondingly non-aqueous agent containing an ammonium ion instead of a water treatment with polar solvents by unit ion. Thus, the pH value within the aluminum silicate and the liquid varies within fairly wide limits, depending on the agent in a closed container, which has the ratio of silicon to aluminum. In cases _{where I0} autogenous pressure is maintained, be done. In a similar manner in which the liquid agent contains an acid and treatments can be applied which are unfavorable to the core structure of the aluminum, which include fusion or vapor phase contact, a liquid agent can be made from, for example, provided that the melting point or the references of an evaporated Ammonium compound vaporization temperature of the acid or of the ammo, such as ammonium chloride, or of a denium compound is below the decomposition temperature of aqueous or non-aqueous aluminum silicate containing the same.

Middle. In this way, an aluminum silicate, a variety of acidic compounds can be used as a source

which is otherwise unsuitable for treatment with hydrogen ions, such as chlorine

an acidic liquid agent, very slightly active hydrogen, nitric acid, sulfuric acid and carbon

fourth are useful catalysts 20 acid as well as monocarboxylic acid, dicarboxylic acid

to achieve settings. and polycarboxylic acid, the aliphatic, more aromatic

When carrying out the treatment with or may be cycloaliphatic in nature. Other

liquid means includes the mode of operation employed are compounds that can be employed

bringing the aluminum silicate into contact with inorganic or organic ammonium salts, such as

the desired liquid agent or agents, and 25 ammonium chloride or ammonium hydroxide,

until metallic cations, which can originate from a multitude of metallic compounds

borrowed in aluminum silicate, practically with ease as a source of metallic cations

are exhausted. Group IA metal cations are used, both inorganic and

of the periodic system, if modified, organic salts of the metals of groups IB

Aluminum silicate present, tend to include cat- 30 to VIII of the periodic table

suppress or are lytic properties.

limit, whose activity is generally with an- Typical of the salts that are used the increasing content of these metallic cations are chlorides, bromides, iodides, carbonates, leaves. A treatment with the liquid agent bicarbonate, sulfate, sulfide, thioxynate, dithiozur Achievement of a modified aluminum silicate 35 carbamate, peroxysulfate, acetate, benzoate, citrate, of high catalytic activity is self-evident. Fluorides, nitrates, nitrites, formates, propionates, buses with the duration of the treatment and the tyrate, valeriate, lactate, malonate, oxalate, PaI temperatures, at which it is performed, mitates, hydroxides or tartrates. The only ones to vary. Elevated temperatures tend to limit the particular metal speed applied To speed up the treatment, 40 salts or the metal salts are the ones that they are in that during their duration inversely soluble with the concentrate in which they are used Tration of the ions in the liquid medium varies. Im need to be and that they deal with the hydrogen general are the temperatures used tolerate the ion source, especially if both, the under the ambient room temperature of 24 ° C metal salt and the hydrogen ion source to be in up to temperatures which are below the decomposition 45 of the same liquid agent. The preferred temperature of the aluminum silicate. Subsequently added salts are the chlorides, nitrates and acetates to the fluid treatment will be the treated and sulfates.

Aluminum Silicate Washed With Water, Preferred Of The Great Variety Of Metallic Salts,

wisely with distilled water until the drain washing which can be used are the

water has a pH of wash water, d. H. 50 most preferred salts are those of the trivalent metal,

between about 5 and 8. The aluminum silicate - then that of the bivalent and finally that of the single

material is then based on its content of metallic valuable metal. Of the bivalent metals

Ions by methods known in the art are preferred those of Group IIA of the Peri-

analyzed. The analysis also includes the analytical systems. The are particularly preferred

sizing the runoff water for anions, which are 55 salts of the rare earth metals including cerium,

The result of the treatment in washing is achieved by Lanthanum, Praseodymium, Neodymium, Illinois, Samarium,

as well as the determination and correction of Europium, Gadolinium, Terbium, Dysprosium, HoI-

Anions made up of soluble substances or cerium, erbium, thulium, ytterbium and cassio-

Settlement products of insoluble products in peium.

the drainage water has entered and the otherwise in the 60 The aluminum silicates treated in this way can

Aluminum silicate present as both naturally and synthetically with amorphous impurities

are. or crystalline structure. This aluminum

The actual working method used for the silicates can be a three-dimensional latticework

Execution of the liquid treatment of the aluminum, SiO ₄ and A10 ₄ tetrahedra are described,

Miniumsilikats can be in a continuous or 65 in which the tetrahedron is transversely divided by

discontinuous processes exist that at atmo- the proportional oxygen atoms, whereby the ratio

spherical, below atmospheric or above atmospheric of all aluminum and silicon atoms

spherical pressure lying pressure carried out oxygen atoms 1: 2. In their hydrated

7 8

Form can represent the aluminosilicates by the following of M and y can be any value from 0 to 7 Formula can be represented: can.

The formula for zeolite D, expressed in oxide-M ₂ O: Al ₂ O ₃ : w SiO ₂ : yH ₂ O molar ratios, can be represented as follows:

. . ". '. , t,., · T ₃₁₁₊ ι ⁵ 0.9 ± 0.2 [xNa ₂ O: (lx) K ₂ O]: Al ₂ O ₃ : wSiO ₂ : yH ₂ O

where M em is the cation, which is the electrovalence

of the tetrahedron, η is the valence of the cation where χ means a value from 0 to 1, w 4.5 to

represents w is the moles of SiO ₂ and y is the moles of about 4.9 and y is in the fully hydrated form

H ₂ O are. The cation can be any one or more of approximately 7.

of a number of metal ions, namely in 10 Other synthetic crystalline aluminum silicones

Depending on whether the aluminum silicate syn- kates that can be used include those

is thetted or occurs naturally. Typical ones referred to as R, S, T, Z, E ₁ F, Q and B as zeolites

Cations include sodium, lithium, and others.

Potassium, silver, magnesium, calcium, zinc, barium, the formula for Zeolite R can be used in oxide

Iron and manganese. Although the ratios are written as follows:

organic oxides in silicates and their spatial _±

loan arrangement may vary, with certain> ^ j. y y. y y.

Properties in the aluminum silicates stand out- where w is 2.45 to 3.65 and y in the hydrated

are called, the two main characteristics are shape roughly 7 means.

of these materials the presence of at least 20 The formula for zeolite S can be expressed in Oxydmolver-

0.5 equivalent of an ion of positive valence per gram proportions can be written as

atom aluminum in its molecular structure r> a j-m-nt «r \ -Air»., "a. "U r>

,. _, ..,. ,. . ,. τ-, λ ,, ■ ■ u, y ± u, z INa ₇ U .AI9Uq. woiUi. yjnuu

and an ability to cope with dehydration

without significantly influencing the SiO ₄ - and AlO ₄ - where w is 4.6 to 5.9 and y is the hydrated

To undergo scaffolding. In that regard, these 25 shape are roughly 6 to 7's.

Properties to achieve a catalyst combination The formula for Zeolite T can be used in Oxydmolver-

High activity compositions according to the invention can be written as follows:

essentially 1.1 ± 0.4 xNa ₂ O: (lx) K ₂ O: A1 ₂ O ₃ :

Typical materials include synthesized, kri- ^z 6 9 + 05 SiO · ν HO

stallinic aluminum silicates, referred to as zeolite X- 30 '' ² ' ²

net, which as the molar ratio of oxides as follows where χ is any value from about 0.1 to un-

can be represented: approximately 0.8 means and y is any value from approximately 0 to 8.

1.0 ± 0.2 M ^ O: Al ₂ O ₃ : 2.5 ± 0.5 SiO ₂ : y H ₂ O _The formula for zeolite Z can be expressed in Oxydmolver-

35. conditions are written as follows:

where M is a cation with a valence not K O -Al O -2SiO · νHO

is more than 3, η represents the valence of M and 2-23-2 · y 2

y is a value up to 8, depending on the identity where Y is any value not exceeding 3,

The formula for zeolite E can be expressed in Oxydmolver-

stalls. The sodium form can be written as a 4 ° molar ratio Oxides can be represented as follows:

0.9 Na ₂ O: Al ₂ O ₃ : 2.5 SiO ₂ : 6.1 H ₂ O ° ^{9 ± 0} ^ ^ O: Al ₂ O ₃ : 1.95 ± 0.1 SiO ₂ : y H ₂ O

Another synthesized crystalline aluminum, where M is a cation, η the valence of the cation minium silicate, referred to as zeolite A, can represent 45 and y is a value from 0 to 4. are put in molar ratios of the oxide as: The formula for zeolite F can be written in oxide molar ratios as follows: 1.0 ± 0.2 M ₂ O: Al ₂ O ₃ : 1.85 ± 0.5 SiO ₂ : y H ₂ O

" 0.95 ± 0.15 M ₂ O: Al ₂ O ₃ : 2.05 ± 0.3 SiO ₂ : y H ₂ O

where M represents a metal, η the valence of 5 °

M and y is any value up to about 6. As where M is a cation, η prepares the valence of the cation, zeolite A contains primarily sodium denotes and y means any value from 0 to about 3 cations and is referred to as sodium zeolite A. Has.

Other suitable synthesized crystalline alu- The formula for zeolite Q expressed in oxydminium silicates are those that are called zeolites Y, L and D 55 molar ratios, can be written as are designated.

The formula for zeolite Y, expressed in 0.95 ± 0.05 M ₁ O: Al ₂ O ₃ : 2.2 ± 0.05 SiO ₂ : y H ₂ O oxide mole ratios, is as follows: "

...... Air »er> u n> where M is a cation, η the valency of the cation

U, y ± Ό, ζ Ma ₂ U: Al ₂ U ₃ : wbiU ₂ : y _{denotes H 2} U _{6o and y has} any value from 0 to 5.

where w is a value between 3 and 6, and the formula for zeolite B can be expressed in Oxydmolver-

y can be a value up to approximately 9. conditions are written as:

The composition of zeolite L can be im

Oxide molar ratio can be represented as follows: 1> ° ^± °> ² M ₂ O: Al ₂ O ₃ : 3.5 ± 1.5 SiO ₂ : y H ₂ O

1.0 ± 0.1 M ₁ O: Al ₂ O ₃ : 6.4 ± 0.5 SiO ₂ : y H ₂ O where M represents a cation, η the valence of the

"Is cation and y has an average value of 5.1

where M denotes a metal, π has the valence, but can be 0 to 6.

Among the naturally occurring crystalline aluminum silicates that are used to manufacture of the catalysts used according to the invention can be applied include levynite, erionite, Faujasite, analcite, paulingite, noselite, ferriorite, heulandite, scolecite, stilbite, clinoptilolite, harmotome, phillipsite, Brewsterite, flaktite, datolite and the following aluminum silicates:

Chabazit ..
Gmelinite ..
Cancrinite.

Leucite

Lazurite
Scapolit ..
Ptilolite ....
Mesolite
Mordenite.,
Nepheline ..
Natrolite ..
Sodalite ...

Na ₂ O-Al ₂ O ₃ -4SiO ₂ -6H ₂ O

Na ₂ O-Al ₂ O ₃ -SiO ₂ -OH ₂ O

3 (Na ₂ O • Al ₂ O ₃ • 2SiO ₂ ) • Na ₂ CO ₃

K ₂ O-Al ₂ O ₃ -4SiO ₂

(Na, Ca) ₅ Al ₆ Si ₆ O ^ 2 (S, Cl, So ₄ )

Na ₄ Al ₃ Si ₉ O ₂₄ • Cl

10SiO ₂ -4H ₂ O
3SiO ₂ -2-3H ₂ O
10SiO ₂ -OH ₂ O
2SiO ₂

IO

Na ₂ O
Na ₂ O
Na ₂ O
Na ₂ O

Al ₂ O ₃
Al ₂ O ₃
Al ₂ O ₃
Al ₂ O ₃

Na ₂ O-Al ₂ O ₃ • 3SiO ₂ • 2H ₂ O
3 (Na ₂ O-Al ₂ O ₃ · 2SiO ₂ ) · 2NaCl

Other aluminosilicates that can be used are etched clays.

Of the clay materials, the montmorillonite and kaolin groups are comparable types which include the sub-bentonites, such as bentonite, and the kaolins, commonly referred to as Dixie, McNamee, Georgia and Florida clays, in which the main mineral component is halloysite, kaolinite, Is dickite, nacrite or anauxite. Such clays can be used in their originally mined raw state or initially subjected to calcining, acid treatment or chemical modification. However, in order to make the keys for the use of suitable, the clay material with sodium hydroxide or potassium hydroxide, preferably in mixture with a SiIiciumdioxydquelle, such as sand, or sodium silicate Siliciumdioxydgel treated and calcined at 110-871 ⁰ C. After calcining, the molten material is crushed, dispersed in water and leached in the resulting alkaline solution. During the leaching process, materials with different degrees of crystallinity are crystallized out of the solution. The solid material is separated from the alkaline material and then washed and dried. The treatment can be carried out by reacting mixtures, which have the following weight ratios:

Na ₂ O / clay (dry basis).
SiO ₂ / clay (dry basis) ..
H ₂ 0 / Na ₂ O (molar ratio)

1.0 to 6.6: 1
0.01 to 3.7: 1
35 to 180: 1

55

The active aluminum silicates that are used for the preparation of the catalysts used according to the invention are used are characterized in that they are 0.5 to 1 equivalent of an ion more positive Have valence per gram atom of aluminum, as recognized by base exchange with other cations Working methods was determined. Aluminum silicate starting material that does not have these properties but can also be used provided it has either been pretreated or acquired these properties as a result of treatment with an agent. Example one Pretreatment: The contact of clayey materials with caustic or caustic-silica mixtures leads to the formation of amorphous and / or crystalline aluminum silicates with at least 0.5 equivalent, usually about 1.0 equivalent of cation per gram atom of aluminum. In a similar way Way leads the treatment of an amorphous silica-alumina composition with a liquid agent containing an ammonium ion convertible into a hydrogen ion, e.g. B. tetramethylammonium hydroxide, to an increase in the concentration of the cation per gram atom of aluminum to values above 0.5 equivalents.

Although the aluminosilicate component contains varying amounts of silicon and aluminum has been found to give extraordinarily good results through the use of crystalline Aluminum silicates can be obtained that have atomic ratios of silicon to aluminum which are greater than 1.1 and preferably greater than 1.67 and even more preferably greater than 2.7. Preferred aluminum silicates are natural materials such as gmelinite, chabazite and mordenite, and synthetic crystalline aluminum silicates such as zeolites X, Y and T.

The aluminum silicate active ingredient prepared in the manner described above is combined, dispersed or otherwise intimately admixed with an inorganic oxide gel that acts as a base, binder, carrier or conveyor is used, and in proportions such that the resulting product is in the final Composition about 2 to 95 weight percent and preferably about 5 to 50 weight percent of the aluminum silicate contains. The resulting composition of aluminum silicate and inorganic Oxide gel is then preferably precalcined in an inert atmosphere at temperatures close to those that are intended for conversion, but can also initially during use are calcined in the conversion process. In general, the catalyst composition is between 66 to 316 ° C dried and then calcined, either in air or in an inert atmosphere of nitrogen, hydrogen, helium, Flue gas or another inert gas in temperature ranges from about 260 to 816 ° C during a Periods of one to 48 hours or more. It goes without saying that the aluminum silicate active ingredient can be calcined prior to its introduction into the inorganic oxide gel.

The composition of aluminum silicate and inorganic oxide gel can be made by several methods processed, whereby the aluminum silicate, which has a grain size of less than 40 μ and is preferably within a range of 2 to 7 microns, intimately with the inorganic oxide gel is mixed while the latter is in an aqueous state, e.g. B. in the form of a Hydrosols, hydrogels, wet gelatinous precipitates, or a mixture thereof. Thus can finely divided active aluminum silicate are mixed directly with a silica-containing gel, which through Hydrolyzing a basic solution of alkali metal silicate with an acid such as hydrogen chloride or sulfuric acid. The mixing of the two ingredients can be done in any way be carried out, such as. B. in a ball mill or other type of kneading machine. That

809 508/314

Aluminum silicate can also be dispersed in a hydrosol made by reacting an alkali metal silicate with an acid or an alkaline coagulant. The hydrosol is then given the opportunity to become in Solidify mass into a hydrogel, which is then dried and broken into pieces of the desired shape or through a nozzle in an oil bath or other water-immiscible suspending agent dispersed to give spherical "pearl" particles of a catalyst like this in U.S. Patent 2,384,946. The resulting aluminum silicate-containing silica Gel is washed free of soluble salts and • then dried and / or, if desired, calcined. The total content of the resulting composition of alkali metal including alkali metals, that may originally be present in the aluminum silicate is less than about 4% and preferably less than about 3 percent by weight based on the total composition.

Similarly, the active aluminum silicate can be mixed with an aluminum-containing oxide will. Such gels are known and can e.g. B. be prepared by adding ammonium hydroxide or ammonium carbonate to a salt of nitrate in an amount sufficient to make aluminum hydroxide to form, which is converted into aluminum oxide after drying. The aluminum silicate can be mixed with the aluminum-containing oxide, while the latter is in the form of a Hydrosols, hydrogel or wet gelatinous precipitate is present.

The inorganic oxide gel can also consist of a multiple gel (multicomponent gel) which comprises a predominant amount of silicon dioxide with one or more metals or oxides thereof from groups IB, II, III, IV, V, VI, VII and VIII of the periodic table. The multiple gel of silicon dioxide with metal oxides of groups IIA, III B and IVA of the Periodic Table is particularly preferred, the metal oxide being magnesium oxide, aluminum oxide, zirconium oxide, beryllium oxide or thorium oxide. The multiple gel makeup is well known and generally involves either separate precipitation or co-precipitation operations in which a suitable salt of the metal oxide is added to an alkali metal silicate and a base or acid is added as needed to precipitate the corresponding oxides. The silicate content of the silica-containing gel carrier provided here is generally within the range of 55 to 100 percent by weight with a metal oxide content in the range of 0 to 45% Small amounts of promoters or other materials that may be present in the composition include cerium, Chromium, cobalt, _c tungsten, uranium, platinum, lead, zinc, calcium, magnesium, lithium, nickel and their compounds as well as silicon dioxide-aluminum oxide or other silicon-containing oxide combinations as fine particles.

In a further embodiment according to the invention, aluminum silicate catalysts can with unusually high activity due to the incorporation of a metal aluminum sihcatate into an inorganic one Oxydgelträger are prepared, after which the aluminum silicate with the above-mentioned agent, containing a hydrogen ion or an ammonium ion convertible into a hydrogen ion, in contact is brought. The treatment is carried out for a sufficiently long period of time as described above Conditions for obtaining active aluminum silicates carried out. It was determined, that in this way processed catalysts in hydrocarbon conversions and in particular are unusually active in the cracking of hydrocarbon oils, with extraordinarily high Ratios of gasoline to low quality products such as coke and gas can be achieved.

It has further been found in accordance with the invention that catalysts of improved activity and with other advantageous properties in the conversion of hydrocarbons are obtained by subjecting the treated aluminosilicate to a mild steam treatment at elevated temperatures of 427 to 816 ° C, preferably at temperatures from about 538 to 704 ^° C. The treatment can take place in an atmosphere of 100% steam or in an atmosphere consisting of steam and a gas which is essentially inert to the aluminum silicate. The steam treatment evidently produces advantageous properties in the aluminum silicate.

The high catalytic activities that are achieved with the aluminum silicates processed in this way are particularly evident in the cracking of a hydrocarbon feed. In the following examples, the catalyst used consists of a conventional silica-alumina cleavage catalyst of the "pearl" type. The silicon dioxide-aluminum oxide catalyst contains approximately 10 percent by weight Al ₂ O ₃ and the remainder SiO ₂ . In some cases it also contains traces of Cr ₂ O ₃ , ie about 0.15 percent by weight.

The cleavage activity of the catalyst is further demonstrated by its ability to catalyze the conversion of a Mid-Continent gas oil having a boiling range of 232-510 ⁰ C, to gasoline, which has an end point of 210 ⁰ C. Vapors of the gas oil are passed through the catalyst at temperatures of 468 or 482 ° C., predominantly under atmospheric pressure, at a feed rate of 1.5 to 16.0 volumes of liquid oil per volume of catalyst per hour for 10 minutes. This experiment with this catalyst served to compare the various product yields achieved with such catalysts with yields of the same products obtained with conventional silica-alumina catalysts at the same level of conversion. The differences (Δ values) shown below represent the yields achieved with the catalyst used according to the invention minus the yields achieved with conventional catalysts .

Those carried out using catalysts used in the process of the invention Cleavage mode of operation can take place at temperatures ranging from approximately 371 to 649 ° C at negative pressure, atmospheric Pressure or pressure above atmospheric pressure. The catalyst can be in Shape of arranged in a fixed bed, spherical particles or pearls can be used

or in the case of flow processes in which the catalyst is arranged in a reaction zone, to which the catalyst is continuously added and from which it is continuously removed. A particularly effective cleavage process can be achieved if the catalyst with a movable bed is used, as is the case with the "Thermofor cracking process" known method is provided.

In the following are some embodiments for the production of those to be used according to the invention Given catalysts. For the preparation of the catalyst is within the scope of the invention no protection claimed.

The invention is further illustrated by examples.

Working method A

A synthetic crystalline aluminosilicate referred to as zeolite 13X was twelve 2-hour treatments with an aqueous solution containing a mixture of 5 percent by weight of chlorides of rare earths and 2 weight percent of ammonium chloride at 82 ⁰ C, subjected. The aluminum silicate was then washed with water until no chloride ions were found in the flow of water, was then dried and thereafter treated at 663 ⁰ C for 20 hours with 100% atmospheric steam, in order to obtain a catalyst with a sodium content of 0.31 percent by weight .

example 1

The table below shows the cleavage values that were achieved when the according to procedure A obtained catalyst for the cracking of gas oil at 482 ° C was applied.

Table I.

Split values

Conversion, volume percent 60.9

Liquid space flow velocity

time / hour 16

10 Reid vapor pressure, gasoline, volume percent 54.6

Excess Q products, volume percent 9.5

C ₅ + gasoline, volume percent 51.7

Total C ₄ products, volume percentage 12.5

Dry gas, weight percent 5.6

Coke, weight percent 2.3

H ₂ , weight percent 0.02

J advantage

10 Reid vapor pressure, volume percent +9.3 excess C ₄ products, volume percent -4.5

C ₅ + gasoline, volume percentage +7.4

Total Q products, volume percent -3.7

Dry gas, weight percent -2.2

Coke, weight percent -2.4

Working method B

Procedure A was repeated with the modification that the crystalline aluminum silicate one continuous treatment for 24 hours instead of twelve 2 hour treatments was subjected.

B e i s ρ i e 1 2

The table below shows the catalyst obtained according to procedure B using the catalyst values obtained for the cracking of gas oil at 482 ° C.

Table II
Cleavage data

Conversion, volume percent 60.7

Fluid space disturbance velocity

time / hour 16

10 Reid vapor pressure, gasoline,

Volume percent 51.7

Excess Cr products, 11.2% by volume

C ₅ + gasoline, percent by volume 49.2

Total C ₄ products, volume percent 13.7

Dry gas, weight percent 6.4

Coke, weight percent 3.0

H ₂ , weight percent 0.03

J advantage

10 Reid vapor pressure, gasoline,

Volume percentage +6.5

Excess Ct products, volume percent -2.8

C ₅ + gasoline, volume percentage +6.2

Total Cr products, volume percent -2.5

Dry gas, weight percent -1.3

Coke, weight percent -1.7

Working method C

A crystalline aluminum silicate, designated Zeolite 13X, was subjected to three 2-hour treatments with a 5% by weight aqueous solution of ammonium chloride and then treated for 48 hours with an aqueous solution consisting of a 5% by weight solution of rare earth chlorides and 2% by weight of an ammonium chloride . The aluminum silicate was then washed with water until no chloride ions in the effluent water were longer exists, dried and for 24 hours at a temperature of 649 ⁰ C with steam at 1.05 kg / cm ^2, to a catalyst with a sodium content of 0 To achieve 2 percent by weight.

Working method D

A natural Crystalline aluminum silicate, referred to as gmelinite, was added to a particle size that was smaller than the mesh size of a sieve having a mesh count of 144 per square centimeter, crushed and calcined in air for 2 hours at 343 ⁰ C. 5 g of the calcined, comminuted gmelinite were then treated 10 times with 10 ecm of a solution which contained 4 percent by weight of a mixture of rare earth chlorides and 1 percent by weight of ammonium chloride. Each of these treatments lasted 1 hour at a temperature of 114 to 121 ° C. The aluminum silicate was then washed with water until the drainage water no longer contained chloride ions, dried overnight, and. crushed at 123 ° C,

turn to a particle size that is smaller than the clear mesh size of a sieve with a Mesh count of about 20 per square centimeter was crushed and kept at 482 ° C for 3 hours calcined in air.

Example 3

The catalyst prepared according to procedure D was used for the cleavage of decane at a Catalyst concentration of 3.3 ecm and a feed rate of 3.0 V / V / hour. (fluid) and a temperature of 482 ° C. A conversion of 91.6 weight percent was found achieved.

Working method E

Procedure D was repeated with the modification that Ptitolit instead of Gmelinit was applied.

Example 4

The catalyst prepared according to procedure E was used for the cleavage of decane. The conversion was 58.7 percent by weight.

Example 5

Under the conditions shown below, the catalyst activity in benzene-ethylene alkylation of a catalyst to be used in the present invention with that of a conventional one Catalyst compared. The results also shown below were obtained.

Conditions:

Temperature 213 ° C

Atmospheric pressure

Benzene-ethylene ratio

(molar) 12/1

Benzene space velocity,

Volume of benzene / volume

Catalyst / hour 12

treated with monium chloride. The product was washed with water until the liquid drained off contained no more chloride ions, dried and then added with steam for 20 hours Treated 663 ° C under atmospheric pressure. The resulting aluminum silicate contained 0.36 percent by weight Sodium and 24.6 percent by weight rare earths, determined as rare earth oxide.

Example 6

Toluene was dealkylated to benzene by adding 60 cm ³ / min. helium saturated with toluene at room temperature passed over a sample of 3 ml of the catalyst prepared according to procedure F at 538 ° C. for 1 hour.

Working method G

A synthetic crystalline aluminum silicate called Zeolite 13 X (0.9 Na ₂ O: Al ₂ O ₃ : 2.5 SiO ₂ : 6.1 H ₂ O) was treated at 82 ° C. with an aqueous solution containing 5 Treated percent by weight rare earth chloride hexahydrate and 2 percent by weight ammonium chloride. The rare earth chloride solution consisted essentially of the chlorides of lanthanum, cerium, neodymium and praseodymium with smaller amounts of samarium, gadolinium and yttrium. A 20 weight percent aqueous slurry of the aluminum silicate was placed in each of three vessels connected in series. The rare earth chloride solution was poured into the first vessel at a rate large enough to replace all of the solution in the three vessels once every hour. The liquid flowing out of the third vessel was continuously filtered and. the filter cake is recycled to the first vessel. The treatment was carried out for 24 hours, after which the treated material was washed free of chloride, dried at 121 ° C. and calcined at 538 ° C. for 3 hours. Analysis of the end product showed 0.22 percent by weight sodium and 26.5 percent by weight rare earths, determined as rare earth oxide.

With rare earths 90 Silica exchanged zeolite X ¹ Aluminum oxide Operating time, minutes .... 90 Product analysis, weight 91.2 percent 8.4 benzene 0.4 100.0 Ethylene benzene 100.0 0.0 Other alkylbenzenes ² ) .. 0.0 91.5 100.0 Conversion of ethylene to ethylbenzene,% 0.0

Example 7

η-hexane was hydroisomerized using a liquid phase procedure. The isomerization was at a temperature of 204 ° C under a pressure of 281 atm and using a hexane space velocity of 0.10 v / v / hr. and a hydrogen-hexane ratio of 1.5: 1 mol, the catalyst prepared according to procedure G being used became. The results listed in the table below were obtained by analyzing the Product obtained with a temperature programmed gas chromatograph.

¹ J 26.5 percent by weight (SE) ₂ O ₃ ; 0.22 percent by weight Na,
13X zeolite.

² ) diethylbenzenes and toluene.

Working method F

Flow time / hours

A synthetic, crystalline aluminum silicate with a low boiling point The name Zeolite 13 X was continuously 65 constituents with an aqueous solution containing

5 percent by weight of a mixture of rare hemisobutane

Earth chloride hexahydrate and 5 percent by weight am- η-butane

Analysis of the gas used

(Weight percent)

0.05
0.05

Analysis of the product after

4 hours

Flow time

(Weight percent)

1.2 • 9.6 0.8

continuation

Flow time hours

Analysis of the gas used

! (Weight percent)

Analysis of the
Product

4 hours

Flow time

(Weight percent)

Isopentane - n-pentane - 2,2-dimethylbutane. - 2,3-dimethylbutane + 2-methyl- pentane 0.1 3-methylpentane ... 4.2 η-hexane 94.3 Not determined ... - Not determined ... 0.3 Not determined ... 1.0

9.1
1.1

3.2

20.0
9.9

39.9
0.7
3.8
0.7

As can be seen from the above values, the catalyst according to the invention is still active in the liquid phase isomerization of η-hexane at extremely low temperatures. At 204 ^° C., 58 percent by weight of the hexane in the material used was converted with good selectivity.

Working method H

A synthetic, crystalline aluminum silicate called Zeolite 13 X became a continuous one Treatment with an aqueous solution containing 5 percent by weight of lanthanum chloride

hexahydrate and 2 percent by weight ammonium chloride at 82 ° C. The aluminum silicate was then washed with water until no chloride ions were more in the effluent, and then dried for 20 hours at 663 ⁰ C with 100% ethyl treated atmospheric water vapor. The result was a catalyst with a sodium content of 0.36 percent by weight and a lanthanum content of 26.2 percent by weight.

Example 8

Using the catalyst prepared according to Procedure H, catalytic reforming was carried out carried out. The results listed in the table below were obtained. The reforming reaction was carried out at or near atmospheric pressure.

IO conditions:

Temperature, "C 382.6

Hourly liquid

Room flow velocity .. 0.70

Use / catalyst V0I./V01 4.2

Products:

C ₄ + volume percent 102.1

C ₅ + volume percent 83.9

Octane R + 3 91.1

Q, volume percent 5.7

Coking product,

Weight percent 1.0

H ₂ Cl, C ₂ , weight percent 0.3

Claims (5)

Patent claims: 1. Process for the catalytic conversion of a hydrocarbon feed by contacting of the hydrocarbons under conversion conditions with a catalyst, characterized in that one an at least partially crystalline aluminosilicate used as a catalyst, the 0.5 to 1.0 equivalents per gram atom of aluminum of ions of positive valence, consisting of 0.01 to 0.99 equivalents Hydrogen ions per gram atom of aluminum and 0.99 to 0.01 equivalents of cations of metals from groups IB to VIII of the Periodic Table per gram atom of aluminum, contains. 2. The method according to claim 1, characterized in that a catalyst is used in which the amount of alkali metal is less than 0.25 equivalent per gram atom of aluminum. 3. The method according to claim 1 or 2, characterized in that an aluminosilicate is used, which contains 0.8 to 1.0 equivalents of positive valence ions per gram atom of aluminum. 4. The method according to any one of claims 1 to 3, characterized in that there is a catalyst used in which the aluminosilicate is distributed in an inorganic oxide gel. 5. The method according to any one of claims 1 to 4, characterized in that there is a catalyst used, in which the aluminosilicate is an atomic ratio of silicon to aluminum greater than 1.6. Considered publications:
German Auslegeschrift No. 1 094 389;
U.S. Patent Nos. 2,916,437, 2,960,478, 2,971,903, 2,971,904.